WO2023190605A1 - Matériau composite et son procédé de production, et agent de réticulation - Google Patents

Matériau composite et son procédé de production, et agent de réticulation Download PDF

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WO2023190605A1
WO2023190605A1 PCT/JP2023/012683 JP2023012683W WO2023190605A1 WO 2023190605 A1 WO2023190605 A1 WO 2023190605A1 JP 2023012683 W JP2023012683 W JP 2023012683W WO 2023190605 A1 WO2023190605 A1 WO 2023190605A1
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group
polymer
composite material
guest
host
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PCT/JP2023/012683
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Japanese (ja)
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義徳 ▲高▼島
明 原田
峻秀 朴
優作 河合
昌明 金
康正 大橋
宏明 ▲高▼橋
基史 大▲崎▼
和也 高橋
瑛規 白川
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国立大学法人大阪大学
ユシロ化学工業株式会社
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Publication of WO2023190605A1 publication Critical patent/WO2023190605A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • C08L5/16—Cyclodextrin; Derivatives thereof

Definitions

  • the present invention relates to a composite material, a method for producing the same, and a crosslinking agent.
  • Polymer materials are widely applied, for example, to films, adhesives, coating agents, molding raw materials, paints, etc., and are indispensable functional materials in fields such as electronic parts, automobile parts, and packaging materials. Particularly in recent years, as products with higher performance and higher precision are required to be provided in various fields, polymer materials are also required to have even higher performance and functionality. Research and development of molecular materials is actively conducted. In particular, improving the hardness, elongation, and fracture energy resistance of polymeric materials is extremely important from the viewpoints of improving product performance and life, reducing environmental impact, and utilizing resources.
  • Patent Document 1 or Patent Document 2 relates to precise control of polymer structure using host-guest interactions by inclusion complexes in order to provide polymer materials with high mechanical strength etc. Techniques have also been proposed.
  • the present inventors have discovered that the above object can be achieved by using a cyclic molecular multimer, and have completed the present invention.
  • Item 1 comprising a cyclic molecular multimer having at least two host groups and a polymer component
  • the host group is a group obtained by removing one hydrogen atom or hydroxyl group from cyclodextrin or a cyclodextrin derivative
  • the cyclic molecular multimer is a composite material having a structure in which at least two of the host groups are connected by a group having a chain structure with a valence of two or more.
  • Section 2 In the cyclodextrin derivative, the hydrogen atom of at least one hydroxyl group of the cyclodextrin is substituted with at least one group selected from the group consisting of a hydrocarbon group, an acyl group, and -CONHR (R is an alkyl group).
  • Item 1 The composite material according to item 1, having a structure.
  • Section 3 Item 3. The composite material according to item 1 or 2, comprising a crosslinked structure in which the polymer component is crosslinked by the cyclic molecular multimer.
  • the polymer component includes a guest polymer having at least one guest group on a polymer side chain, At least one host group in the cyclic molecular multimer forms an inclusion complex with a guest group in the guest polymer, and the other host group forms an inclusion complex with a guest group in another guest polymer.
  • Item 3. The composite material according to item 1 or 2, comprising a crosslinked structure formed by forming a crosslinked structure.
  • the polymer component includes a first linear polymer, At least one host group in the cyclic molecular multimer is penetrated by the first linear polymer, and another host group is penetrated by another first linear polymer.
  • Item 3. The composite material according to item 1 or 2, comprising a structure.
  • the polymer component includes a second linear polymer; 6.
  • Section 7 A crosslinking agent for forming a crosslinked structure of a polymer, the crosslinking agent comprising:
  • the crosslinking agent contains a cyclic molecular multimer,
  • the cyclic molecular multimer has at least two host groups, The host group is a group obtained by removing one hydrogen atom or hydroxyl group from cyclodextrin or a cyclodextrin derivative,
  • the cyclic molecular multimer is a crosslinking agent having a structure in which at least two of the host groups are connected by a group having a chain structure with a valence of two or more.
  • Item 8 In the cyclodextrin derivative, the hydrogen atom of at least one hydroxyl group of the cyclodextrin is substituted with at least one group selected from the group consisting of a hydrocarbon group, an acyl group, and -CONHR (R is an alkyl group).
  • Section 9 A method for producing a composite material according to any one of items 1 to 6, comprising: A method for producing a composite material, comprising the step of obtaining a composite material from a mixture of the cyclic molecular multimer and a polymer component.
  • Item 10 A method for producing a composite material according to any one of items 1 to 6, comprising: A method for producing a composite material, comprising producing a polymer component by performing a polymerization reaction of a polymerizable monomer in the presence of the cyclic molecular multimer to obtain a composite material.
  • the composite material of the present invention can be produced by a simple method and has excellent mechanical properties.
  • FIG. 2 is a schematic diagram schematically showing a crosslinked structure in which a guest polymer is crosslinked by a cyclic molecular multimer.
  • FIG. 2 is a schematic diagram schematically showing a crosslinked structure in which a first linear polymer is crosslinked by a cyclic molecular multimer.
  • This is a reaction scheme for producing a cyclic molecular multimer.
  • 1 is a 1 H-NMR spectrum of the cyclic molecular polymer obtained in Production Example 2.
  • 3 shows the results of GPC measurement of the cyclic molecular multimer obtained in Production Example 2. These are the stress-strain curves, Young's modulus, and fracture energy results of the composite materials obtained in Examples 1-1, 1-2, and 1-3.
  • Example 2-1 and Comparative Example 2-1 These are the stress-strain curves, Young's modulus, and fracture energy results of the composite materials obtained in Example 2-1 and Comparative Example 2-1. These are the results of Young's modulus and fracture energy of the composite materials obtained in Example 3-1 and Comparative Example 3-1. These are the stress-strain curves, Young's modulus and fracture energy results of the composite materials obtained in Examples 4-1, 4-2, 4-3 and Comparative Example 4-1. These are the stress-strain curves, Young's modulus, and fracture energy results of the composite materials obtained in Example 5-1 and Comparative Example 5-1.
  • the composite material of the present invention includes a cyclic molecular multimer having at least two host groups and a polymer component.
  • the host group is a group obtained by removing one hydrogen atom or hydroxyl group from cyclodextrin or a cyclodextrin derivative.
  • the cyclic molecular multimer has a structure in which at least two of the host groups are connected by a group having a chain structure with a valence of two or more.
  • the composite material of the present invention is a polymer-based composite material (polymer composite material), which can be produced by a simple method and has excellent mechanical properties.
  • the composite material of the present invention has high fracture energy.
  • the cyclic molecular multimer contained in the composite material of the present invention is a compound having at least two host groups, and has a structure in which at least two of the host groups are connected by a group having a chain structure of divalent or higher valence. It is something that you have.
  • the cyclic molecule multimer contained in the composite material of the present invention will be referred to as "cyclic molecule multimer C.”
  • the host group is a group obtained by removing one hydrogen atom or hydroxyl group from cyclodextrin or a cyclodextrin derivative.
  • the cyclodextrin derivative has a structure in which at least one of the hydroxyl groups of cyclodextrin has a hydrogen atom substituted with a hydrophobic group. That is, a cyclodextrin derivative refers to a molecule having a structure in which a cyclodextrin molecule is substituted with another hydrophobic organic group. However, the cyclodextrin derivative has at least one hydrogen atom or at least one hydroxyl group, preferably at least one hydroxyl group.
  • the hydrophobic group preferably has a structure substituted with at least one group selected from the group consisting of a hydrocarbon group, an acyl group, and -CONHR (R is a methyl group or an ethyl group).
  • R is a methyl group or an ethyl group
  • the aforementioned "at least one group selected from the group consisting of a hydrocarbon group, an acyl group, and -CONHR (R is a methyl group or an ethyl group)" will be referred to as a "hydrocarbon group, etc.” for convenience. It may be written down.
  • cyclodextrin in this specification means at least one member selected from the group consisting of ⁇ -cyclodextrin, ⁇ -cyclodextrin, and ⁇ -cyclodextrin.
  • the cyclodextrin derivative is at least one selected from the group consisting of ⁇ -cyclodextrin derivatives, ⁇ -cyclodextrin derivatives, and ⁇ -cyclodextrin derivatives.
  • the host group is a monovalent or higher valence group obtained by removing one hydrogen atom or hydroxyl group from a cyclodextrin derivative, but the hydrogen atom or hydroxyl group removed in the cyclodextrin derivative can be removed from any part of the cyclodextrin or cyclodextrin derivative. It may be.
  • the cyclodextrin derivative has carbonized hydrogen atoms of up to N-1 hydroxyl groups per cyclodextrin molecule. It is formed by being substituted with a hydrogen group, etc.
  • the host group is a monovalent group obtained by removing one "hydrogen atom" from a cyclodextrin derivative
  • the cyclodextrin derivative has a structure in which the hydrogen atoms of up to N hydroxyl groups per molecule of cyclodextrin are hydrocarbons. It may be substituted with a group, etc.
  • the host group is a group obtained by removing one hydrogen atom or hydroxyl group from a cyclodextrin derivative
  • 70% or more of the hydrogen atoms of the hydroxyl groups out of the total number of hydroxyl groups present in one molecule of cyclodextrin are the hydrocarbons. It is preferable to have a structure substituted with a group, etc., more preferably 80% or more, and particularly preferably 90% or more of the total number of hydroxyl groups.
  • the host group is a cyclodextrin derivative with one hydrogen atom or hydroxyl group removed
  • the hydrogen atoms of 13 or more hydroxyl groups out of all the hydroxyl groups present in one molecule of ⁇ -cyclodextrin are carbonized. It is preferable to have a structure substituted with a hydrogen group or the like, more preferably 15 or more, and particularly preferably 17 or more.
  • the host group preferably has a structure in which 15 or more hydroxyl hydrogen atoms out of all the hydroxyl groups present in one molecule of ⁇ -cyclodextrin are substituted with the hydrocarbon group, etc., and 17 or more is more preferable. Preferably, 19 or more are particularly preferable.
  • the host group preferably has a structure in which 17 or more hydrogen atoms of all the hydroxyl groups present in one molecule of ⁇ -cyclodextrin are substituted with the hydrocarbon group, etc., and 19 or more is more preferable. Preferably, 21 or more are particularly preferable.
  • the type of the hydrocarbon group is not particularly limited.
  • the hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl group.
  • the number of carbon atoms in the hydrocarbon group is not particularly limited, and for example, it is preferable that the hydrocarbon group has 1 to 4 carbon atoms.
  • hydrocarbon group having 1 to 4 carbon atoms examples include methyl group, ethyl group, n-propyl group, isopropyl group, and butyl group.
  • hydrocarbon group is a propyl group or a butyl group, it may be either linear or branched.
  • examples of the acyl group include an acetyl group, propionyl group, and formyl group. It is easy to form host-guest interactions or other polymer chains can easily penetrate inside the host group ring, and it is easy to obtain polymeric materials with excellent toughness and strength.
  • the acyl group is preferably an acetyl group.
  • -CONHR (R is a methyl group or an ethyl group) is a methyl carbamate group or an ethyl carbamate group. It is easy to form host-guest interactions or other polymer chains can easily penetrate inside the host group ring, and it is easy to obtain polymeric materials with excellent toughness and strength.
  • -CONHR is preferably an ethyl carbamate group.
  • the hydrocarbon group, etc. is preferably an alkyl group or acyl group having 1 to 4 carbon atoms, preferably a methyl group and an acyl group, more preferably a methyl group, an acetyl group, or a propionyl group, and a methyl group or an acetyl group. is particularly preferred.
  • the cyclic molecule multimer C has a group having a chain structure with a valence of two or more.
  • the group is hereinafter referred to as a "linking group".
  • the linking group is for linking at least two of the host groups.
  • the linking group is divalent or more, preferably tetravalent or less, and more preferably divalent.
  • linking group is not particularly limited.
  • the linking group may be linear or branched.
  • the molecular weight of the linking group is preferably 12 or more, preferably 50 or more, more preferably 100 or more, and preferably 10,000 or less, more preferably 3,000 or less, It is more preferably 1000 or less, particularly preferably 500 or less.
  • the terminal portion of the linking group is bonded to the host group.
  • the linking group is divalent, both ends of the linking group are bonded to the host group.
  • the bond between the linking group and the host group is a chemical bond, usually a covalent bond.
  • the cyclic molecular multimer C can be represented by the following general formula (1), for example. R 1 -(R H ) n (1)
  • R 1 represents a linking group
  • R H represents the host group
  • n is an integer of 2 to 4.
  • the compound represented by formula (1) has n R H covalently bonded to R 1 .
  • the host group R H in the host group-containing polymerizable monomer represented by formula (1) is an example of a monovalent group obtained by removing one hydroxyl group from cyclodextrin or a derivative thereof. .
  • R 1 is a divalent linking group
  • the cyclic molecular polymer C can be represented by the following general formula (1a).
  • R 1 represents a linking group
  • R H represents the host group.
  • the host group R H in the host group-containing polymerizable monomer represented by formula (1a) is an example of a monovalent group obtained by removing one hydroxyl group from cyclodextrin or a derivative thereof. .
  • the linking group (R 1 ) can have, for example, an alkylene group, an ether group, a thioether group, an amino group, a disulfide group, or the like.
  • the number of carbon atoms in the alkylene group is, for example, preferably 1 or more, more preferably 2 or more, and preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. It is preferable that the linking group (R 1 ) has at least an alkylene group.
  • the linking group (R 1 ) can have one or more groups consisting of an alkylene group having 1 to 5 carbon atoms, an ether group (-O-), and a thioether group (-S-). .
  • the linking group (R 1 ) can also include all of these groups.
  • the linking group (R 1 ) can have a group represented by the following general formula (2).
  • m is an integer of 1 to 5, preferably 2 to 4, and more preferably 2.
  • k is an integer of 1 to 5, preferably 1 to 3, and more preferably 1.
  • l is an integer of 1 to 5, preferably 1 to 3, and more preferably 1.
  • a is an integer of 1 to 5, preferably 1 to 3, and more preferably 2.
  • b is an integer of 1 to 5, preferably 1 to 3, and more preferably 1.
  • c is an integer of 1 to 5, preferably 1 to 3, and more preferably 1.
  • the terminal portion of the linking group (R 1 ) is not particularly limited in type as long as it is a group capable of bonding to a host group, and may have, for example, a hydroxyl group, a thiol group, or one or more substituents.
  • Alkoxy group, thioalkoxy group which may have one or more substituents, alkyl group which may have one or more substituents, amino group which may have one substituent , a divalent group formed by removing one hydrogen atom from a monovalent group selected from the group consisting of an amide group, an aldehyde group, and a carboxyl group which may have one substituent. can be mentioned.
  • the substituents in formulas (1) and (1a) are not particularly limited, and include, for example, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a halogen atom, and a carboxyl group. group, carbonyl group, sulfonyl group, sulfone group, cyano group, etc.
  • the terminal portion of the linking group (R 1 ) is preferably a divalent group formed by removing one hydrogen atom from an amide group which may have one substituent, and It is preferably a divalent group (i.e. -CONH-) formed by removing one hydrogen atom from an amide group which does not have a group, and in this case, the terminal of the linking group (R 1 ) The part becomes -CONH-.
  • the terminal portions of the linking groups (R 1 ) may all be the same or different.
  • both ends may be the same or different.
  • the connecting group (R 1 ) has a group represented by the above formula (2)
  • the terminal portion of the connecting group (R 1 ) is directly bonded to both ends of the group represented by the formula (2). do.
  • R 1 represented by the general formula (1a) is represented by the following formula (2a).
  • the number of host groups is 2 or more, preferably 4 or less, more preferably 3 or less, and even more preferably 2.
  • the method for producing the cyclic molecular multimer C is not particularly limited, and for example, a wide variety of known production methods can be employed.
  • the cyclic molecular polymer C can be produced by a reaction between an acrylated cyclodextrin and a dithio compound having thiol groups at both ends, a so-called thiolene reaction.
  • Acrylated cyclodextrin is, for example, a cyclodextrin compound having a structure in which one of the hydroxyl groups of cyclodextrin or its derivatives is replaced with a (meth)acrylic compound.
  • (meth)acrylic compounds include acrylamide, and in this case, acrylated cyclodextrin is a cyclodextrin having a structure in which one hydroxyl group of cyclodextrin or its derivative is replaced with acrylamide (CH 2 ⁇ CHCONH-). It becomes a dextrin compound.
  • acrylated cyclodextrin include 6-acrylamide cyclodextrin.
  • Acrylated cyclodextrin can be obtained by known methods.
  • (meth)acrylic means “acrylic” or “methacrylic
  • (meth)acrylate means “acrylate” or “methacrylate”
  • (meth)allyl means “ means “allyl” or “methallyl”.
  • the dithio compound has the following general formula (3) HS- ⁇ (C m H 2m ) l -O ⁇ a -(C m H 2m ) b -SH (3)
  • Compounds represented by the following can be mentioned.
  • m, l, a, and b are the same as m, l, a, and b in formula (2), respectively.
  • dithio compounds examples include 3,6-dioxa-1,8-octanedithiol.
  • the method of the thiol-ene reaction is not particularly limited, and for example, a method similar to the known thiol-ene reaction can be employed in the present invention. Examples include a method in which a mixture of the acrylated cyclodextrin and the dithio compound is irradiated with ultraviolet light, or a method in which the acrylated cyclodextrin and the dithio compound are reacted in the presence of an azo compound.
  • polymer component examples of the polymer component included in the composite material of the present invention include a wide range of known polymer compounds.
  • the polymer component is preferably a polymer that can be crosslinked by the cyclic molecular multimer C to form a crosslinked structure. That is, in the composite material of the present invention, it is preferable that the polymer component includes a crosslinked structure formed by crosslinking with the cyclic molecular multimer.
  • Examples of the polymer component that can form the crosslinked structure include a guest polymer and a first linear polymer.
  • Examples of the guest polymer include a polymer compound having at least one guest group in a polymer side chain. Such guest polymers can be exemplified by a wide variety of known guest polymers.
  • the type of the guest group is not limited as long as it is a group that can have a host-guest interaction with the host group, especially a group that is included in the host group.
  • the guest group is not limited to a monovalent group; for example, the guest group may be a divalent group. Further, the guest group-containing monomer unit can contain only one guest group, or can contain two or more guest groups.
  • guest groups include linear or branched hydrocarbon groups having 3 to 30 carbon atoms, cycloalkyl groups, heteroaryl groups, and organometallic complexes, which may have one or more substituents. good.
  • the substituent is the same as the above-mentioned substituent, and includes, for example, a halogen atom (e.g., fluorine, chlorine, bromine, etc.), a hydroxyl group, a carboxyl group, an ester group, an amide group, an optionally protected hydroxyl group, etc. be able to.
  • a halogen atom e.g., fluorine, chlorine, bromine, etc.
  • More specific guest groups include chain or cyclic alkyl groups having 4 to 18 carbon atoms and groups derived from polycyclic aromatic hydrocarbons.
  • the chain alkyl group having 4 to 18 carbon atoms may be either straight chain or branched.
  • the cyclic alkyl group may have a cage structure.
  • Examples of polycyclic aromatic hydrocarbons include ⁇ -conjugated compounds formed by at least two or more aromatic rings, and specifically, naphthalene, anthracene, tetracene, pentacene, benzopyrene, chrysene, pyrene, Triphenylene and the like can be mentioned.
  • guest groups include, for example, alcohol derivatives; aryl compounds; carboxylic acid derivatives; amino derivatives; azobenzene derivatives having a cyclic alkyl group or phenyl group; cinnamic acid derivatives; aromatic compounds and their alcohol derivatives; amine derivatives; ferrocene derivatives; azobenzene; naphthalene derivative; anthracene derivative; pyrene derivative; perylene derivative; clusters composed of carbon atoms such as fullerene; A monovalent group formed by removing an atom) can also be mentioned.
  • guest group examples include t-butyl group, n-octyl group, n-dodecyl group, isobornyl group, adamantyl group, pyrene-derived groups, and groups to which the above substituents are bonded.
  • the number of guest groups contained in the guest polymer may be only one, or two or more.
  • Examples of the guest polymer include a copolymer of a polymerizable monomer having a guest group (guest group-containing monomer unit) and a polymerizable monomer not having a guest group.
  • the guest group-containing monomer unit is not particularly limited as long as it is a compound that has the above-mentioned guest group and has polymerizability.
  • the guest group-containing polymerizable monomer preferably has a functional group having radical polymerizability.
  • the guest group-containing polymerizable monomer examples include vinyl-based polymerizable monomers having the guest group.
  • the guest group-containing polymerizable monomer can include a compound represented by the following general formula (g1).
  • Ra represents a hydrogen atom or a methyl group
  • RG represents the guest group
  • R 2 represents a hydroxyl group, a thiol group, an alkoxy group which may have one or more substituents, Thioalkoxy group which may have one or more substituents, alkyl group which may have one or more substituents, amino group which may have one substituent
  • 1 represents a divalent group formed by removing one hydrogen atom from a monovalent group selected from the group consisting of an amide group, an aldehyde group, and a carboxyl group which may have a substituent.
  • guest group-containing polymerizable monomers include n-hexyl (meth)acrylate, n-octyl (meth)acrylate, n-dodecyl (meth)acrylate, adamantyl (meth)acrylate, and (meth)acrylate.
  • Hydroxyadamantyl acrylate 1-(meth)acrylamidoadamantane, 2-ethyl-2-adamantyl(meth)acrylate, N-dodecyl(meth)acrylamide, t-butyl(meth)acrylate, 1-acrylamidoadamantane, N- (1-adamantyl) (meth)acrylamide, N-benzyl (meth)acrylamide, N-1-naphthylmethyl (meth)acrylamide, ethoxylated o-phenylphenol acrylate, phenoxypolyethylene glycol acrylate, isostearyl acrylate, nonylphenol EO adduct
  • Examples include acrylate, isobornyl (meth)acrylate, (meth)acrylate having a pyrene moiety, and (meth)acrylamide having a pyrene moiety.
  • the guest group-containing polymerizable monomer can be produced by a known method. Moreover, a commercially available product can also be used as the guest group-containing polymerizable monomer.
  • the type of polymerizable monomer that does not have a guest group is not particularly limited, and for example, a wide range of known polymerizable monomers can be mentioned.
  • a polymerizable monomer having no guest group is hereinafter referred to as a "third polymerizable monomer.” It is also preferable that the third polymerizable monomer does not have a host group.
  • Examples of the third polymerizable monomer include various known vinyl polymerizable monomers. Specific examples of the third polymerizable monomer include compounds represented by the following general formula (a1).
  • Ra is a hydrogen atom or a methyl group
  • R3 is a halogen atom, a hydroxyl group, a thiol group, an amino group that may have one substituent or a salt thereof, and one substituent. It represents a carboxyl group or a salt thereof which may have one, an amide group or a salt thereof which may have one or more substituents, and a phenyl group which may have one or more substituents.
  • the hydrogen atom of the carboxyl group is a hydrocarbon group having 1 to 20 carbon atoms, a hydroxyalkyl group (for example, a hydroxymethyl group, a 1- hydroxyethyl group, 2-hydroxyethyl group), methoxypolyethylene glycol (the number of ethylene glycol units is 1 to 20, preferably 1 to 10, particularly preferably 2 to 5), ethoxypolyethylene glycol (the number of ethylene glycol units is 1 to 20, preferably 1 to 10, particularly preferably 2 to 5), Examples include carboxyl groups (ie, esters) substituted with 1 to 20 groups, preferably 1 to 10 groups, particularly preferably 2 to 5 groups.
  • the hydrocarbon group having 1 to 20 carbon atoms preferably has 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, and particularly preferably 1 to 3 carbon atoms.
  • the hydrocarbon group may be either straight chain or branched.
  • R 3 when R 3 is an amide group having one or more substituents, that is, a secondary amide or a tertiary amide, one hydrogen atom or two hydrogen atoms of the primary amide
  • examples include amide groups in which atoms are independently substituted with hydrocarbon groups having 1 to 20 carbon atoms or hydroxyalkyl groups (eg, hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group).
  • the hydrocarbon group having 1 to 20 carbon atoms preferably has 1 to 15 carbon atoms, and preferably 2 to 10 carbon atoms.
  • the hydrocarbon group may be either straight chain or branched.
  • the monomer represented by formula (a1) include (meth)acrylic acid, allylamine, maleic anhydride, styrene, methyl (meth)acrylate, ethyl (meth)acrylate, (meth)acrylate, etc.
  • n-propyl acrylate isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, hexyl (meth)acrylate, (meth)acrylate cyclohexyl acid, n-octyl (meth)acrylate, 2-methoxy (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 2-phenylethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-methoxy( meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 2-phenylethyl (meth)acrylate, hydroxymethyl (meth)acrylate, phenoxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, ethoxy-diethylene glycol (meth)acrylate (Met
  • the third polymerizable monomer is preferably (meth)acrylic acid, (meth)acrylic acid ester, (meth)acrylamide, or a derivative thereof.
  • the guest polymer can be formed by polymerizing the polymerizable monomer having the guest group and the third polymerizable monomer. Therefore, the guest polymer has the polymerizable monomer unit having the guest group and the third monomer unit.
  • the content of the guest group in all structural units thereof is preferably 0.1 mol% or more, more preferably 0.3 mol% or more, and 0.5 mol% or more. More preferably, it is 1 mol% or more.
  • the content ratio of the guest groups in all the structural units thereof is preferably 40 mol% or less, more preferably 20 mol% or less, and 10 mol% or less. is more preferable, and particularly preferably 5 mol% or less.
  • the content ratio of each structural unit in the polymer is determined by the usage ratio of each polymerizable monomer used during polymerization. It can be considered that the molar ratio of
  • the first linear polymer examples include linear polymers that can penetrate the inside of the ring of the host group.
  • the first linear polymer is preferably a vinyl polymer, particularly a polymer obtained by radical polymerization, among which (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, ) It is more preferable to use one or more polymers selected from the group consisting of propyl acrylate, (meth)acrylamide, and N,N-dimethyl(meth)acrylamide.
  • first linear polymer examples include condensation polymer compounds and polycondensation polymer compounds, such as epoxy resins, polycarbonate resins, polyamide resins, polyester resins, polyurethane resins, and urea resins. It will be done. Specifically, polyurethanes having structural units derived from chain diol compounds and chain diisocyanate compounds can be mentioned.
  • the first linear polymer can also have in its polymer chain a monomer unit S having a size that cannot penetrate into the ring of the host group.
  • the monomer unit S acts as a so-called stopper and can prevent the first linear polymer from falling off from the host group.
  • the mechanical properties of the composite material are greatly improved, making it tougher. It can easily be used as a material.
  • the polymerizable monomer for forming the monomer unit S is not particularly limited as long as it has a size that cannot penetrate into the ring of the host group, for example, the number of carbon atoms of the group bonded to the ester oxygen
  • Examples include (meth)acrylic esters having 4 or more and 30 or less, styrene, N-substituted (meth)acrylamides having an alkyl group of 2 or more and 30 or less carbon atoms, and the like.
  • Examples of (meth)acrylic esters in which the group bonded to the ester oxygen has 4 or more and 30 or less carbon atoms include (meth)acrylic acid alkyl esters having an alkyl group having a linear, branched, or cyclic structure.
  • the number of carbon atoms in the alkyl group is preferably 4 or more and 20 or less, more preferably 5 or more and 14 or less.
  • the polymerizable monomers for forming the monomer unit S include n-butyl (meth)acrylate, i-butyl (meth)acrylate, t-butyl (meth)acrylate, and n-(meth)acrylate. -heptyl, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, and the like.
  • the monomer unit S is preferably contained in an amount of 0 to 10 mol%, more preferably 0 to 5 mol%, in the first linear polymer.
  • the crosslinked structure is formed by crosslinking the polymer component with the cyclic molecular multimer C, as described above, and in particular, the crosslinked structure is formed by crosslinking the polymer component with the guest polymer and/or the first linear polymer.
  • a crosslinked structure is likely to be formed.
  • the polymer component includes the guest polymer
  • at least one host group in the cyclic molecular multimer forms an inclusion complex with a guest group in the guest polymer
  • Other host groups can include crosslinked structures formed by forming inclusion complexes with guest groups in other guest polymers.
  • crosslinked structure A such a crosslinked structure will be referred to as "crosslinked structure A.”
  • the composite material of the present invention is characterized in that the linear polymer passes through at least one host group in the cyclic molecular multimer, and , other host groups can include crosslinked structures through which other linear polymers pass.
  • crosslinked structure B such a crosslinked structure will be referred to as "crosslinked structure B.”
  • the crosslinked structure A has a structure in which the guest polymer is crosslinked by a cyclic molecular multimer C.
  • FIG. 1 is a schematic diagram schematically showing the structure of the crosslinked structure A.
  • the cyclic molecular polymer C can function as a crosslinking agent that crosslinks guest polymers.
  • one host group of the cyclic molecular multimer C includes the guest group of the guest polymer (a so-called host-guest interaction is formed).
  • the other host group of the cyclic molecular polymer C includes the guest group of another guest polymer.
  • a crosslinked structure A is formed.
  • the cyclic molecular multimer C can crosslink a certain guest polymer with another guest polymer different from this guest polymer.
  • the crosslinked structure A is formed by host-guest interaction, that is, the crosslinked structure is formed by reversible bonding.
  • the composite material containing the crosslinked structure A has host-guest interaction, and therefore can have self-healing properties.
  • the composite material containing the crosslinked structure A has, for example, greatly improved mechanical properties compared to the guest polymer alone (i.e., non-crosslinked guest polymer), and in particular, has a fracture energy that is significantly improved compared to the guest polymer alone. This is a very noticeable improvement. Therefore, the composite material containing the crosslinked structure A is a strong material.
  • the content ratios of the cyclic molecular polymer C and the guest polymer are not particularly limited.
  • the content of the cyclic molecule polymer C is preferably 0.5 to 40% by mass, more preferably 2 to 20% by mass, based on the total mass of the cyclic molecule polymer C and the guest polymer, More preferably, it is 5 to 10% by mass.
  • the guest group when the host group is derived from an ⁇ -cyclodextrin derivative, the guest group is preferably at least one selected from the group of octyl group and dodecyl group, and the host group is When the host group is derived from a ⁇ -cyclodextrin derivative, the guest group is preferably at least one selected from the group consisting of an adamantyl group and an isobornyl group, and when the host group is derived from a ⁇ -cyclodextrin derivative, the guest group is an octyl group or a dodecyl group. At least one selected from the group consisting of , cyclododecyl group, and adamantyl group is preferred.
  • the polymer component may contain a polymer other than the guest polymer, or the polymer component may consist only of the guest polymer.
  • the crosslinked structure B has a structure in which the first linear polymer is crosslinked by a cyclic molecular multimer C.
  • FIG. 2 is a schematic diagram schematically showing the structure of the crosslinked structure B.
  • the cyclic molecular polymer C can function as a crosslinking agent that crosslinks guest polymers.
  • the first linear polymer passes through the ring of one host group of the cyclic molecular multimer C.
  • the other host group of the cyclic molecular multimer C passes through the other first linear polymer.
  • a crosslinked structure B is formed.
  • the cyclic molecular multimer C can crosslink a certain first linear polymer and a different first linear polymer.
  • the crosslinked structure B is formed by the first linear polymer penetrating the inside of the host group ring, that is, a movable crosslinked structure is formed.
  • the composite material containing the crosslinked structure B has, for example, greatly improved mechanical properties compared to the first linear polymer alone, and in particular, has significantly improved fracture energy compared to the first linear polymer alone. This will improve the results. Therefore, the composite material containing the crosslinked structure B is a strong material.
  • the content ratios of the cyclic molecular polymer C and the first linear polymer are not particularly limited.
  • the content of the cyclic molecule polymer C is preferably 0.5 to 40% by mass, and preferably 2 to 20% by mass, based on the total mass of the cyclic molecule polymer C and the first linear polymer. is more preferable, and even more preferably 5 to 10% by mass.
  • the polymer component can also include a second linear polymer.
  • the second linear polymer can also penetrate the network of the crosslinked structure B. This increases the compatibility with the first linear polymer and the second linear polymer, and the composite material has particularly excellent mechanical strength and tends to be a tougher material.
  • the second linear polymer is preferably linear when penetrating the network of the crosslinked polymer.
  • the type of the second linear polymer is not particularly limited as long as it can penetrate the network of the crosslinked structure B, and for example, the same types as the first linear polymer can be mentioned.
  • the first linear polymer and the second linear polymer may be the same or different.
  • the second linear polymer can also contain the monomer unit S like the first linear polymer.
  • the polymer component can include a polymer other than the first linear polymer and the second linear polymer, or the polymer component can include a polymer other than the first linear polymer and the second linear polymer. It may consist only of a linear polymer, and furthermore, the polymer component may consist only of the first linear polymer and the second linear polymer.
  • the composite material of the present invention is a polymer composite material containing a cyclic molecular multimer C and a polymer component.
  • the composite material of the present invention includes, for example, the above-mentioned crosslinked structure A or crosslinked structure B, and thereby becomes strong. Note that the composite material of the present invention can also include both the crosslinked structure A and the crosslinked structure B.
  • the composite material of the present invention can also contain other components in addition to the cyclic molecular multimer C and the polymer component, as long as the effects of the present invention are not impaired.
  • the shape of the polymer composite material of the present invention is not particularly limited, and for example, it may be a molded product such as a film, sheet, plate, or block, or it may be in the form of particles, fibers, granules, pellets, etc. There may be.
  • the polymer composite material of the present invention configured as described above, has excellent mechanical strength and tends to be a strong material. Specifically, the polymer composite material of the present invention tends to have high values for both fracture energy and Young's modulus, and because the two are well balanced, it becomes a strong material.
  • Step 1 Obtaining a composite material from a mixture of a cyclic molecular multimer and a polymer component.
  • the polymer composite material of the present invention can be manufactured by a method comprising Step 2 below.
  • Step 2 A step of producing a polymer component by performing a polymerization reaction of a polymerizable monomer in the presence of a cyclic molecular multimer to obtain a composite material.
  • the composite material containing the crosslinked structure A can be manufactured by any manufacturing method including the step 1 or the step 2, and the composite material containing the crosslinked structure B can be manufactured by the method including the step 1 or the step 2 described above.
  • the manufacturing method can be manufactured by any manufacturing method including either the step 1 or the step 2 described above.
  • the manufacturing method of the present invention includes step 1, the above-mentioned crosslinked structure A is easily formed, so it is suitable as a method for manufacturing a composite material containing the crosslinked structure A.
  • the manufacturing method of the present invention includes Step 2
  • the above-mentioned crosslinked structure B is likely to be formed, so it is suitable as a method for manufacturing a composite material containing the crosslinked structure B.
  • Step 1 The cyclic molecule multimer used in step 1 is the same as the cyclic molecule multimer C described above.
  • the cyclic molecule multimer used as a raw material in Step 1 it is preferable that no polymer or guest group is penetrated or included in the ring of at least one host group of the cyclic molecule, and that no polymer or guest group is included in the ring of at least one host group of the cyclic molecule. It is more preferable that no polymer or guest group be passed through or included in the polymer.
  • the polymer component used in step 1 is the same as the polymer component used to form the crosslinked structure A described above. Therefore, the polymer component used in step 1 includes the guest polymer.
  • the method for preparing the mixture of the cyclic molecular polymer C and the guest polymer is not particularly limited.
  • a mixture can be obtained by mixing the cyclic molecular polymer C and the guest polymer in an organic solvent. Therefore, the mixture can be a solution or a dispersion, preferably a solution.
  • the mixing means is also not particularly limited, and for example, a wide variety of known mixing means can be used.
  • organic solvents examples include hydrocarbon solvents such as benzene, toluene, and xylene; ketone solvents such as acetone, methyl ethyl ketone, and isophorone; alcohol solvents such as tert-butyl alcohol, benzyl alcohol, phenoxyethanol, and phenylpropylene glycol; Halogenated hydrocarbon solvents such as methylene and chloroform; Ether solvents such as 1,2-dimethoxyethane, tetrahydrofuran, 1,4-dioxane, and anisole; Ethyl acetate, propyl acetate, butyl acetate, ethyl carbitol acetate, butyl carbide Examples include ester solvents such as toll acetate; amide solvents such as N,N-dimethylformamide and N,N-dimethylacetamide; carbonate solvents such as dimethyl carbonate, diethyl carbonate, and propylene carbonate.
  • the method for obtaining the composite material from the mixture is not particularly limited.
  • a solid composite material can be formed by evaporating the organic solvent of the mixture.
  • a composite material on a film can be formed by casting the mixture.
  • the conditions of the casting method are not particularly limited either, and a wide variety of known casting methods can be employed.
  • the crosslinked structure A is formed by the above step 1. That is, by mixing the cyclic molecule multimer C and the guest polymer, an inclusion complex is formed between the host group in the cyclic molecule multimer C and the guest group in the guest polymer, thereby forming a crosslinked structure. A is formed.
  • the crosslinked structure A obtained in step 1 can be made into a composite material, or a composite material can also be formed by appropriately combining the crosslinked structure A obtained in step 1 and other materials. .
  • Step 2 The cyclic molecule multimer used in step 2 is the same as the cyclic molecule multimer C described above.
  • the cyclic molecule multimer used as a raw material in step 2 it is preferable that no polymer or guest group penetrates or is included in the ring of at least one host group of the cyclic molecule, and that no polymer or guest group is included in the ring of at least one host group of the cyclic molecule. It is more preferable that no polymer or guest group be passed through or included in the polymer.
  • the polymerizable monomer used in step 2 is a polymerizable monomer for forming a polymer component. Therefore, the polymerizable monomer used in step 2 is a polymerizable monomer for producing the first linear polymer.
  • the polymerizable monomers for producing the first linear polymer include (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, (meth)acrylamide, One or more types selected from the group consisting of N,N-dimethyl(meth)acrylamide can be mentioned.
  • a polymerization reaction of the polymerizable monomer is performed in the presence of the cyclic molecule polymer.
  • Such polymerization reaction is not particularly limited, and, for example, conditions for known polymerization reactions can be widely employed in the present invention.
  • the polymerization reaction can be carried out using a mixture of a cyclic molecular polymer and a polymerizable monomer in the presence of a polymerization initiator.
  • a solvent can be used in the polymerization in Step 2, or it can also be carried out without a solvent (for example, bulk polymerization, etc.).
  • the crosslinked structure B is formed by the above step 2. That is, in the presence of the cyclic molecule multimer C, a polymerization reaction of the polymerizable monomer occurs and the growing polymer chain (first linear polymer chain) penetrates the host group in the cyclic molecule multimer C. As a result, a movable crosslinked structure B as shown in FIG. 2 can be formed.
  • the crosslinked structure B obtained in step 2 can be made into a composite material, or a composite material can be formed by appropriately combining the crosslinked structure B obtained in step 2 and other materials. .
  • the second linear polymer can be produced by carrying out a polymerization reaction of the polymerizable monomer for producing the above-mentioned second linear polymer in the presence of the crosslinked structure B.
  • a second linear polymer can penetrate the network of the crosslinked structure B.
  • a crosslinked structure A can be produced.
  • the crosslinked structure A can be produced by performing a polymerization reaction of the third polymerizable monomer in the presence of the clathrate compound.
  • the composite material of the present invention can be manufactured in a simple manner by the manufacturing method comprising Step 1 or Step 2 described above.
  • the present invention also includes crosslinking agents for forming crosslinked structures of polymers.
  • the crosslinking agent contains the cyclic molecular multimer C. That is, the crosslinking agent contains a cyclic molecule multimer, the cyclic molecule multimer has at least two host groups, and the host group has one hydrogen atom or hydroxyl group from cyclodextrin or a cyclodextrin derivative.
  • the cyclic molecule multimer has a structure in which at least two of the host groups are connected by a group having a chain structure with a valence of two or more.
  • the crosslinking agent of the present invention makes it possible to produce a composite material with excellent mechanical properties.
  • a cyclic molecule polymer C was produced by a thiolene reaction between an acrylated cyclodextrin and a dithio compound having thiol groups at both ends.
  • ACCD-S 203 mg, 0.10 mmol
  • 3,6-dioxa-1,8-octanedithiol 9.1 mg, 0.050 mmol
  • IRGACURE1173 registered trademark
  • a cyclic molecule polymer C was produced by a thiolene reaction between an acrylated cyclodextrin and a dithio compound having thiol groups at both ends.
  • ACCD-S (11.0 g, 5.42 mmol) obtained in Production Example 1, 3,6-dioxa-1,8-octanedithiol (0.44 mL, 2.71 mmol)
  • IRGACURE184 (registered trademark) (110 mg, 0.5 mmol) in 55.0 mL of methanol to obtain a solution.
  • FIG. 4 is a 1 H-NMR spectrum of the white solid (main product) obtained in Production Example 2 (for reference, the spectra of the raw material ACCD-S and the dithio compound are also shown). From this figure, it was confirmed that the desired cyclic molecule multimer C (compound represented by the above formula (1a)) was produced. Further, from the results of TLC (not shown) and NMR immediately after the thiolene reaction, it was confirmed that ACCD-S and the dithio compound disappeared, and quantitative progress of the reaction was confirmed. It was found that the NMR integrated intensity value ratio also matched well with the assumed structure.
  • FIG. 5 shows the results of GPC measurement of the white solid (main product) obtained in Production Example 2 (for reference, the GPC measurement results of the raw material ACCD-S and the dithio compound are also shown).
  • a JASCO GPC device was used, the column was Shodex KF-602.5, 602, 601 tandem, the solvent was THF (0.5 mL/min), and the detector was RI. , a peak with a large hydrodynamic radius (10.8 min) corresponding to the target cyclic molecular multimer C was confirmed. Only a small amount of ACCD-S and ACCD-S with crushed vinyl groups were detected (11.
  • Example 1-1 Crosslinked structure A
  • a mixture of the guest polymer and the cyclic molecule polymer C obtained in Production Example 2 was prepared such that the content of the cyclic molecule polymer C obtained in Production Example 2 was 5% by mass. This mixture was added to acetone so that the concentration was 1% by mass, and the mixture was stirred at 25° C. for 4 hours to obtain a solution.
  • the solution was cast in a Teflon (registered trademark) petri dish, left to stand at 25°C for 12 hours, and then left to stand at 100°C for 12 hours to obtain a film.
  • the obtained film was covered with a 4 cm x 4 cm x 0.2 mm spacer and pressed at 2 kN for 4 minutes in an atmosphere of 100° C. to obtain a composite material.
  • Example 1-2 Crosslinked structure A
  • a composite material was obtained in the same manner as in Example 1-1, except that the mixture was prepared such that the content of the cyclic molecular polymer C obtained in Production Example 2 was 10% by mass.
  • Example 1-3 Crosslinked structure A
  • a composite material was obtained in the same manner as in Example 1-1, except that the mixture was prepared such that the content of the cyclic molecular polymer C obtained in Production Example 2 was 20% by mass.
  • Example 2-1 Crosslinked structure B
  • a mixture was obtained by mixing cyclic molecule polymer C and methyl methacrylate (raw material for the first linear polymer) such that the content of cyclic molecule polymer C obtained in Production Example 2 was 10% by mass.
  • Complex formation was promoted by irradiating this mixture with ultrasonic waves for 1 hour to obtain a solution.
  • 0.5 mol % of Omnirad 184 (registered trademark) was added to the solution, and after irradiating with ultrasonic waves for 3 minutes, the solution was placed in a mold, and irradiated with ultraviolet light using a mercury lamp for 60 minutes.
  • the solid material obtained by this irradiation was dried in a vacuum oven at 100° C. to obtain a composite material.
  • Example 2-1 A material was obtained in the same manner as in Example 2-1 except that the cyclic molecular polymer C was not used.
  • Example 3-1 (Example 3-1; Crosslinked structure B) Methyl methacrylate was changed to ethyl acrylate, and a mixture was prepared so that the content of cyclic molecular polymer C was 0.5% by mass, and the amount of Omnirad 184 (registered trademark) was changed to 1% by mole.
  • a composite material was obtained in the same manner as in Example 2-1 except for the following changes.
  • Example 4-1 (Example 4-1; Crosslinked structure B) Methyl methacrylate was changed to methyl acrylate, and a mixture was prepared so that the content of cyclic molecular polymer C was 0.5% by mass, and the amount of Omnirad 184 (registered trademark) was changed to 1% by mole.
  • a composite material was obtained in the same manner as in Example 2-1 except for the following changes.
  • Example 4-2 Crosslinked structure B
  • a composite material was obtained in the same manner as in Example 4-1, except that the mixture was prepared so that the content of the cyclic molecular polymer C was 1% by mass.
  • Example 4-3 Crosslinked structure B
  • a composite material was obtained in the same manner as in Example 4-1, except that the mixture was prepared so that the content of the cyclic molecular polymer C was 3% by mass.
  • Example 5-1 Crosslinked structure B
  • the cyclic molecule polymer C and the mixed monomer of methyl acrylate and hexyl acrylate (of the first linear polymer) were added so that the content of the cyclic molecule polymer C obtained in Production Example 2 was 0.5% by mass.
  • a mixture was obtained by mixing the raw materials (containing 1 mol% hexyl acrylate). Complex formation was promoted by irradiating this mixture with ultrasonic waves for 1 hour to obtain a solution.
  • Omnirad 184 (registered trademark) was added in an amount of 1 mol % to the solution, and after ultrasonic irradiation for 3 minutes, the solution was placed in a mold, and ultraviolet ray irradiation was performed for 30 minutes using a mercury lamp. The solid material obtained by this irradiation was dried in a vacuum oven at 60° C. to obtain a composite material.
  • Example 5-1 A material was obtained in the same manner as in Example 5-1 except that the cyclic molecular polymer C was not used.
  • Figure 6 shows the stress-strain curves (Figure 6(a)) and the Young's modulus and fracture energy results (Figure 6(b)) of the composite materials obtained in Examples 1-1, 1-2, and 1-3. ). From this figure, it can be seen that the composite materials obtained in Examples 1-1, 1-2, and 1-3 have improved Young's modulus and fracture energy compared to the guest polymer alone (Comparative Example 1-1), and are strong. It turned out to be a good material.
  • FIG. 7 shows the stress-strain curves, Young's modulus, and fracture energy results of the composite materials obtained in Example 2-1 and Comparative Example 2-1. This figure shows that the composite material obtained in Example 2-1 has improved Young's modulus and fracture energy compared to the methyl methacrylate monopolymer (Comparative Example 2-1), and is a strong material. Ta.
  • FIG. 8 shows the Young's modulus results of the composite materials obtained in Example 3-1 and Comparative Example 3-1. This figure shows that the composite material obtained in Example 3-1 has improved Young's modulus and fracture energy compared to the ethyl acrylate monopolymer (Comparative Example 3-1), and is a strong material. Ta.
  • Figure 9 shows the stress-strain curves (Figure 9(a)) of the composite materials obtained in Examples 4-1, 4-2, 4-3 and Comparative Example 4-1, and the results of Young's modulus and fracture energy. It is. From this figure, it can be seen that the composite materials obtained in Examples 4-1 to 4-3 have improved Young's modulus and fracture energy compared to the methyl acrylate monopolymer (Comparative Example 4-1), and are strong materials. I found out something.
  • FIG. 10 shows the stress-strain curve (FIG. 9(a)) and the Young's modulus and fracture energy results of the composite materials obtained in Example 5-1 and Comparative Example 5-1.
  • This figure shows that the composite material obtained in Example 5-1 has improved Young's modulus and fracture energy compared to the methyl acrylate/hexyl acrylate polymer (Comparative Example 5-1), and is a strong material.
  • the composite material of Example 5-1 it is presumed that the hexyl acrylate unit in the first linear polymer functions as a stopper, and as a result, further toughening of the composite material could be achieved.

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Abstract

L'invention concerne : un matériau composite qui peut être produit par un procédé simple et présente d'excellentes propriétés mécaniques ; et un procédé de production du matériau composite.　Le matériau composite selon la présente invention comprend un multimère de molécule cyclique ayant au moins deux groupes hôtes et un composant polymère, chacun des groupes hôtes étant un groupe ayant une structure telle qu'un atome d'hydrogène ou un groupe hydroxyle est éliminé de la cyclodextrine ou d'un dérivé de cyclodextrine, et le multimère de molécule cyclique comprend une structure telle que les au moins deux groupes hôtes sont liés l'un à l'autre par l'intermédiaire d'un groupe bivalent ou supérieur ayant une structure linéaire.
PCT/JP2023/012683 2022-03-29 2023-03-28 Matériau composite et son procédé de production, et agent de réticulation WO2023190605A1 (fr)

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CN104861950A (zh) * 2015-05-19 2015-08-26 重庆科技学院 一种超分子线性聚丙烯酰胺驱油剂及其制备方法
JP2019204719A (ja) * 2018-05-24 2019-11-28 株式会社豊田自動織機 自己修復性負極
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JP2008143053A (ja) * 2006-12-11 2008-06-26 Canon Inc インクジェット記録方法
JP2010086864A (ja) * 2008-10-01 2010-04-15 Japan Aviation Electronics Industry Ltd 薄膜アクチュエータ及びこれを用いるタッチパネル
CN104861950A (zh) * 2015-05-19 2015-08-26 重庆科技学院 一种超分子线性聚丙烯酰胺驱油剂及其制备方法
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